Preparation of polyoxymethylene using metal acetylacetonate polymerization catalysts



3,457,227 PREPARATION OF POLYUXYMETHYLENE USING METAL ACETYLACETONATE POLYMERIZA- TION CATALYSTS Carl D. Kennedy, Ponca City, Okla., assignor to Continental Gil Company, Ponca City, Okla, a corporation of Delaware No Drawing. Filed Mar. 11, 1965, Ser. No. 439,090 Int. Cl. C08g 1/02, 1/20 U.S. Cl. 260-67 7 Claims ABSTRACT OF THE DISCLOSURE Trioxane is polymerized or copolymerized with a oxymethylene-containing cyclic ether in the presence of molybdenum dioxydiacetylacetonate as the catalyst to provide a polyoxymethylene exhibiting improved properties.

This invention relates to the preparation of high molecular weight polyoxymethylene. More particularly, the invention relates to the polymerization and copolymerization of trioxane to high molecular weight polyoxymethylene, using as the catalyst molybdenum dioxydiacetylacetonate. In one of its specific, though nonlimiting aspects, the invention relates to the preparation of a new composition of matter which is a polyoxymethylene of improved stability, such improvement in stability resulting from the incorporation in the oxymethylene chain of a carbonyl function group.

It is known that high molecular weight polyoxymethylene can be obtained by contacting trioxane with certain acidic, cationic catalysts including antimony trifiuoride, antimony fluoroborate, bismuth trifiuoride, bismuth oxyfluoride, nickel fluoride, aluminum fluoride, titanium tetrafluoride manganous fluoride, manganic fluoride, mercuric fluoride, silver fluoride, zinc fluoride, ammonium bifluoride, phosphorous pentafluoride, hydrogen fluoride, fluorosulfonic acid, boron trifluoride, and silicon tetrafluoride. The high molecular weight polyoxymethylene can also be obtained by polymerizing formaldehyde With such catalysts as nickel carbonyl, aluminum isopropoxide, activated metallic aluminum, organophosphines, and aluminum chloride.

The present invention comprises a new method for preparing useful, high molecular weight polyoxymethylene, such method being based upon the discovery that molybdenum dioxydiacetylacetonate is a specifically ef fective catalyst for the polymerization of trioxane. When said acetylacetonate is used to catalyze the polymerization of trioxane, most of the resulting polyoxymethylene chains contain a carbonyl group thereby contributing to improved stability of the overall polymeric composition. The carbonyl groups are believed to be loacted at the termini of the oxymethylene chains, instead of the hy droxyl groups which have heretofore constituted the terminal groups characteristic of polyoxymethylene produced from trioxane using other catalyst systems.

Prior work in the field of trioxane polymerization has indicated that certain cyclic ethers can be copolymerized with trioxane to produce a copolymer having better heat stability than the polyoxymethylene produced by the polymerization of substantially pure trioxane monomer. I

itates atent O ice have determined that similar beneficial copolymerization can also be accomplished by the process of the present invention, thus further improving the stability of polymers produced with certain of the metal oxide acetylacetonate catalysts of the invention.

From the foregoing summary description of the invention, it will have become apparent that it is an important object of the invention to produce a novel process for preparing high molecular weight polyoxymethylene.

Another object of the invention is to provide a process for preparing high molecular weight polyoxymethylene of improved thermal stability.

An additional object of the invention is to provide a novel polymeric composition comprising polyoxymethylene units containing at least one carbonyl functional group.

Other objects, as well as certain advantages and salient features, of the invention, will become apparent from the more detailed description of the invention, and the examples of its practice, which hereinafter appear.

As hereinbefore indicated, the process of the present invention comprises contacting certain low molecular weight oxymethylene compounds with the molybdenum complex of the enol form of acetylacetone. The oxymethylene compounds subject to polymerization, trioxane (a cyclic trimer of formaldehyde), and mixtures of trioxane with oxymethylene-containing cyclic ethers having the structural formula wherein R is a divalent oxymethylene group, {O-CHfi, and wherein n is an integer of at least 1, and preferably does not exceed 3. Glycol formal constitutes the most preferred cyclic ether for use in the copolymerization. In the copolymerization of the trioxane and cyclic ether, the mole ratio of cyclic ether to trioxane used is less than 0.5 and is preferably less than 0.2.

The described oxymethylene compounds which are subjected to polymerization in the process of the present invention can, of course, be the pure compounds described, or can conveniently be derived from several other more readily available sources.

Commercially available trioxane of better than 99 percent purity is available and can be used in the trioxane polymerization, although best results are obtained with trioxane purified by recrystallization from petroleum ether or methylene chloride.

It is desirable that all oxymethylene starting materials, the catalysts and polymerization solvents be substantially anhydrous, although minute amounts of moisture can be tolerated.

In the polymerization or copolymerization of trioxane in accordance with this invention, the polymerization is beneficially carried out in a solvent in which the catalyst is soluble, but which is not reactive with either the catalyst or the monomer materials. A number of hydrocarbons, halogenated hydrocarbons and other organic compounds meet the foregoing requirements. Illustrative of suitable solvents are: n-heptane, n-hexane, benzene, toluene, cyclohexane, decahydronaphthalene, methylene chloride, chloroform, carbon tetrachloride, pentane, xylene, nonane and decane, and nitrobenzene. Heptane, cyclohexane and methylene chloride are the preferred solvents.

In addition to solution polymerization of the trioxane, the polymerization of this monomer can be carried out with the monomer in a molten state and without utilizing any solvent. Also, a suspension polymerization of the trioxane can be effected in which the trioxane is insoluble in an inert, non-aqueous liquid reaction medium and is retained in suspension therein, or at least is phased out of solution by cooling during the polymerization procedure. Relatively high viscosity mineral oils and similar nonsolvents for the trioxane can be used in the suspension polymerization procedure, and a suitable surface active agent, can be used to disperse the particles more finely.

When polymerizing trioxane in the presence of solvent, maximum yields of polyoxymethylene are realized at a ratio of 2 ml. solvent to 1 gram of trioxane or less. For most applicable solvents, the preferred ratio of solvent to trioxane ranges from about 0.125 to about 0.5 ml./ gram.

In the case of the trioxane polymerization, from IX mole percent to about 10 mole percent of the catalyst should be employed (based on the mole equivalents of trioxane subjected to polymerization). Preferably from about 1 10 to about 1.0 mole percent of the catalyst is utilized.

Trioxane has a melting point of 64 C. and a boiling point of about 110 C., but the suspension type polym erization of this material can be carried out at temperature as low as 55 C. Melt polymerization of the trioxane can also be carried out with the trioxane super-cooled below its normal melting point prior to addition of the catalyst. Also, operating under superatmospheric pressures, temperatures as high as 120 C. can be employed during the polymerization, provided the pressure is sufiicient to retain the trioxane in the liquid state. In the preferred solution polymerization, the temperature range is preferably maintained from about 65 C. to about 100 C.

Pressure is not critical in the polymerization of the trioxane. Thus, while it is generally preferred to conduct the trioxane polymerization at a superatmospheric pressure either atmospheric, superatmospheric or subatmospheric pressures can be employed.

After completion of the polymerization reactions, the polyoxymethylene polymer is contacted with ammonium hydroxide to remove entrained catalyst therefrom. Preferably, this purification treatment of the polymer is carried out at ambient temperatures to avoid a tendency toward decomposition.

The following examples are given to illustrate the polymerization of trioxane using molybdenum dioxydiacetylacetonate as the polymerization catalyst in accordance with this invention.

In the majority of the examples, the polymerizations were carried out in beverage bottles which were thoroughly cleaned, oven dried and flushed with argon. Either molten trioxane injected into the bottle with a hot syringe or crystalline trioxane was then added to the bottle. In general, the trioxane, or the trioxane-solvent mixture was heated to melt or solution, respectively, prior to addition of the catalyst. After catalyst addition, the bottle was then immediately capped with a neoprene septum and heated in a constant temperature oil bath at C. The reaction bottle and its contents were left in the oil bath for 15 minutes after the reaction period occurred.

Two methods for treatment of the polyoxymethylene polymer with ammonium hydroxide were used. In the first method the polymer was permitted to stand at room temperature with four to five times its weight of NH OH in a beaker for from 1 to 12 hours. In the second method the polymer was placed in a sealed beverage bottle with four to five times its weight of NH OH and heated from 30 minutes to several hours in a 100 oil bath. Whichever of the above methods were used, the product mixture was filtered, washed twice with twenty times its original weight of water, and finally with acetone or methanol to facilitate drying. The product was then oven dried at approximately 50-60 C.

The thermal stability tests (K were run by measuring the percent weight loss per minute at 222. The rates were measured at the fiat portion of a plot of percent weight loss vs. time.

Where the procedures or materials employed departed from those described above, the nature of such departures are described in the examples.

EXAMPLES 1-10 These examples illustrate the effect of varying the relative amounts of solvent and trioxane on the yield and inherent viscosity of the polymer product. All of these polymerizations as set forth in Table I were run in sealed beverage bottles and the molar ratio of catalyst to trioxane used in each example was 4.5 l0- except in Example 6 where the molar ratio was 5 l0 The inherent viscosities were run on NH OH treated products which were acetate capped.

TABLE I Percent Ml. cycloyield of hexane] NHsOH g. tritreated Inherent oxane product viscosity 0 50 0. 58 0. 77 1. 2G 0. 125 78 0. 250 74 1. 29 0. 250 74 l 0. 500 48 1. 57 O. 500 52 0. 75 56 1. 83 1. O0 17 1. 00 14 1 At a ratio of 5.0X10- moles of catalyst to trioxane and this solventratio 93% yield was obtained using trioxane recrystallized from H 601; The trioxane used for the above experiments was recovered from the filtrate from trioxane recrystallized in 112C01 EXAMPLES l119 The polymerization runs described in Table II illustrate the eifect of varying the molar ratio of the molybdenum dioxydiacetylacetonate to trioxane on the yield and properties of the polymer product. Each of the polymerization runs was carried out in a sealed beverage bottle. Except in the one run indicated, 0.22 mole of trioxane was used in each polymerization and 2 grams of triox-ane Was used for each ml. of the cyclohexane solvent employed.

2 Two moles trioxane was used in this experiment.

6 EXAMPLES 20-32 use in the polymerization procedure. The runs were made These examples demonstrate that ,trioxane can be in sealed beverage bottles using 0.22 mole of rtrioxane polymerized in the molten State i h absence f 1. except where md1cated, and the reaction mlxtures were vent) with molybdenum dioxydiacetylacetonate. Some of heated in an oil bath at 100 C. The results of these the polymerization runs were carried out at room tem- 5 polymerization are set forth in Table IV.

TABLE IV Triox- Mole Min.

ane catalyst to re- Percent Solvent (ML) his ory l0- action yield ninh (20) 1. 4 45 65 0. 49 1. 4 13 47 0. 49 1. 4 17 37 0. 21 1. 4 35 2s 0. 51 1. 4 2 0 0) 1. 4 10 0. 51 10) 0. 70 1s 24 0. 70 52 0. as (20) 0. 70 27 62 0. 92 0. 70 29 3s 0. 57 0. 70 5 59 0. 09 0. 70 5 62 0.08 0. 70 s 27 0. 53 (0 0. 70 s 57 0. 12 (20) 0. 35 8 24 0. 10 0. 70 s 60 0. 1s (10) 0. 70 5-7 98 o. 65 0. 70 5-7 51 0. 7s 0. 70 5 78 0. 21 (0 0. 70 12 0. 37

1 Examples 46 and 47 each involved 0.44 mole trioxane.

2 Commercial nonrecrystallized trioxane.

3 The reaction appeared to progress slowly; solid started precipitating at about 20 min.

4 Trioxane was recrystallized from H2CC12. The solvents were freshly distilled prior to use.

5 A difierent batch of commercial trioxane that in was used.

6 Trioxanle was treated by melting commercial trioxane, filtering oft solid material and placing filtrate in reaction Jott es.

perature by super-cooling the molten trioxane. The polyrn- EXAMPLE 53-65 erizsjtions were run in q argon'fiushed P The 40 A series of molybdenum dioxydiace-tylacetonate gfedlents 2 P f 111 each bottle Whlch was Saaled catalyzed trioxane polymerizations were carried out at and heat d in an 0 bath- The results of these P Y atmospheric pressure. The reactions were carried out in ization runs are set forth in Table III. mechanically stirred resin flasks equipped with a con- TABLE III Temp. of Temp. trioxane of when melt catalyst when was reaction Max. temp: Mole Mole cata- Bath temp, added started, reached, Min. to Percent trioxane lyst X10 0. reaction yield mnh Example:

1 Commercial nonreorystallized trioxane was used.

2 RT is a symbol used for room temperature.

3 Commercial trioxane was melted, filtered, and let stand over CaHa at 100 C. for 12 hrs. prior to use.

4 Trioxane used was isolated iron the filtrate of trioxane recrystallization from HzCClz.

EXAMPLES 33-52 denser and a nitrogen flush line and during refluxing of A number of polymerlzatlon runs were earned out for the solvent. The conditlons obtamlng durlng the runs and the purpose of evaluating various types of solvents for 75 the results obtained are set forth in Table V.

TABLE V History of trioxane Moles Example used trioxane Solvent Moles Ml. solvent catalyst X10 Reaction Percent conditions yield Comments 53 0. &4 H6013 36 54 0.67 C014 Initially 150 55 1.0 CCli 150 56 0. [i7 C(Jli 75 57 O. 67 Cyclohcxanc. 75

59 0. (i7 nCsHu 75 62 1. 0 l'lCsI-Iu 125 63 1. 0 nCsHu 125 64 1. 0 nCaH 125 0. 33 llCaHli 40 Cyclohcxanc. 3

1.0 68 Polymerization started within min. after the molybdenum dioxydiacetylacetonato solu. was added. When reaction started, 60 ml. more HOCl was immediately added, and reflux was continued 20 min.

0014 was collected in a Dean-Stark separator. When 26 ml. of C014 (containing some trioxane) had distilled from the mixture, reaction occurred.

Reaction started at about 4 min. after reflux was reached. The mixture was then heated about 3 hr. at reflux.

3.0 23 Polymer started forming at about 2 min.

from addition of molybdenum dioxydiacetylactetonate. The mixture was refluxed for 1 hr. total.

3.0 24 Additional (15 ml.) cyclohexane was added at 2 min. from molybdenum dioxydiacetyb acetonate which was when polymerization seemed to occur. After 8 min. reflux, the reaction was quenched.

3. 0 37 Polymer started forming within 1 min. from addition of molybdenum dioxydiacetylacetonate. Mixture was heated at reflux 6 min. after the polymerization started.

Polymer formation started at about min.

after addition of molybdenum dioxydiacetylaeetonate.

1. 4 When heat was removed and stirring stopped the mixture polymerized within 1 min.

1.4 70 Molybdenum dioxydiacetylacetonate was added to the two phase systems. Which was then vigorously stirred. Reaction occurred within ab out 10 min. from addition of catalyst and seemed to be complete. No heat was applied after addition of molybdenum dioxydiacetylacetonate. Reaction was quenched at 10 min. by addition of acetone.

Reaction occurred within 1 min. from addition of molybdenum dioxydiacetylacetonate in both Examples 80 and 81. No heat was applied after molybdenum dioxydiacyt-lacetonate was added. The reactions were quenched after 30 min. stirring.

Reaction occurred when the misture reached 65. Heating at 65 was maintained for min.

Reaction occurred within 3 min. of molybdenum dioxydiacetylacetonate addition. The stirred reaction mixture was kept at 64 C. for 15 min. after reaction occurred.

1 Commercial untreated monomer trioxane.

The mixture was heated to reflux with N 2 passed through the system, then the catalyst was added as a solution in 1 ml. of hot H0013.

Solid molybdenum dioxydiacetylacetonate was added when the mixture reached reflux.

4 Commercial trioxane was dissolved in warm solvent and filtered into the reaction flask through a buchner funnel.

5 Solvent was gradually removed by distillation. After 20 min. from start of distillation, most or the solvent was removed. Heat was removed.

5 Solution was attained, then the mixture was allowed to cool to 58 0., 3 to 4 degrees below temp. required to form two phases.

EXAMPLES 6676 As has been previously indicated herein, the polyoxymethylene produced by trioxane polymerization using the catayst of the present invention appears to be structurally different from polyoxymethylenes heretofore obtained using catalyst which operates by cationic initiation. The mechanism by which the polymerization proceeds in the present invention is thought to be of an insertion type in which a fragment of the catalyst employed apparently is attached to one end of the growing polymer chain, yielding a chain with an end group other than the hydroxyl group which has heretofore been characteristic of polyoxymcthylcne polymers produced using other known catalysts.

The exact nature of the terminal group which characterizes the polyoxymethylene made by trioxane polymerization in accordance with this invention is not known, but infrared analysis indicates carbonyl group absorption attributable to a part of the polymer produced, and not to residual catalyst. The infrared absorption band is at 1702 cm. (in the carbonyl region) and is not seen in IR analyses of polymer produced from formaldehyde or from trioxane using BF catalyst. In addition to this evidence of partial capping of the polyoxymethylene 60 produced from trioxane by polymerization with a molybdenum dioxydiacetaylacetonate catalyst, a comparison of the inherent viscosity and thermal degradation properties of this polyoxymethylene with the polyoxymethylenes derived from formaldehyde polymerizations in accordance with the process of the present invention shows that a substantial dilference is stability and viscosity exists between the two polymer types. Infrared analysis indicates that the formaldehyde derived polymer is characterized by the conventional hydroxyl end groups. The data set forth in Table VI shows that the polyoxymcthylene derived from molybdenum dioxydiacetylacctonate catalyzed trioxane polymerizations is more stable than the polyoxymethylene derived from the formaledhyde polymerizations. The trioxane-derived polyoxymcthylenes referred t0 in. Table II had lower inherent viscositics than any of the formaldehyde-derived polymers with which they were compared.

when the trioxane is copolymerized with a small amount of glycol formal using the molybdenum dioxydiacetylacetonate catalyst of the invention. Example 77 is a mono- TABLE VI f f polymerization of the trioxane. The other examples illusin in ,0 some Polymer g g g g KW 5 trate the use of various molar ratios of glycol formal to trioxane. Example: I claim \IODA T' 2.82 1. 04 9: iuODa -Ti'i ii 1. 1.47 1. The method of preparing high molecular weight gig? polyoxymethylene comprising contacting, at a tempera- 0 ture of from about 55 C. to 120 C., trioxane as the sole polymerizable material with molybdenum dioxydiacetylacetonate catalyst at a catalyst to trioxane ratio of 2:? at least 1 10- mole of catalyst per mole of trioxane. 76 MODAC-HZCO 0.98 3. 6 2. The method defined in claim 1 wherein said trioxane MODAcis the symbolused tormolybdenum dioxydiacetylacctonate. 'fhssolved an amount j men orgamc Solvent which does not exceed two mill liters of solvent per gram EXAMPLES 77422 of trioxane- 3. The method defined in claim 1 wherein the mole As has previously been indicated herein, it h Ibeen ratio of catalyst to trioxane utilized is from about 1 10* determined that the molybdenum dioxydiacetylacetonate t bo t 0,0-1, catalyst found fifleciive t0 polymerize tTiOXane t0 PQ Y- 4. The method defined in claim 1 wherein the trioxane oxymethylene is also effective to induce copolymerization nd atal t ar contacted at a temperature of from of trioxane and oxymethylene containing cyclic ethers of bout 65 C, to about 100 C. the type hereinbefore de ribed o pr e p y xy 5. The method defined in claim 1 wherein said trioxane ylene copolymers having improved thermal stability. Subis in the liquid state during said contact. stantially the same conditions of polymerization are em- 6. The method defined in claim 2 wherein said inert ployed as are used in the case of the trioxane monomer organic solvent is selected from the group consisting of polymerizations. In the copolymerizations, a molar ratio heptane, hexane and methylene chloride, and the amount of from about 0.01 to 0.2 glycol formal to trioxane can of said solvent employed does not exceed 1.25 milliliters be used, but a substantial improvement in the thermal of solvent per gram of trioxane. stability of the copolymer product can generally be ob- 7. The method defined in claim 1 and further charactained using a molar ratio of from about 0.05 to about terized to include the step of washing the polymer result- 0.15. Examples 77-82 in Table VII demonstrate the iming from said contact with ammonium hydroxide to reprovement in the polymer product which is obtained move residual catalyst therefrom.

TABLE VII Molar Percent total ratio of decomposition Molar ratio glycol at 222 inof catalyst to formalto Percent trioxane X104 trioxane yield M.P.3 inh- K222 15 min. min. Properties Example: 1

77 6.35 0 87 Poor.

6.35 0. 059 83 7 Good. 6.35 0.119 82 4 Do.

4.5 0. 059 87 180 Fair. 4.5 0.119 82 Do. 4.5 0.178 77 Fair-poor.

1 Examples 77-79 were run using trioxane from a different recrystallization than that used for runs 80-82. 2 After NIL-OH treatment and based on combined weights of glycol and trioxane. 5 Recorded M.P. is temperature at which polymer powder first started to melt.

4 The viscosity is substituted here.

5 Determined for the straight line portion after the first 15 minutes.

percent decomposition of this sample was not determined; however, decomposition data for another polymer sample prepared by the same procedure, but from unrecrystallized tri oxane, having the same inherent References Cited UNITED STATES PATENTS 2,989,509 6/1961 Hufgiu et al. 26067 3,194,788 7/1965 Kullmar et al. 26067 3,208,975 9/1965 Vanderberg 26067 3,219,623 11/1965 Berardinelli 26067 3,267,076 8/1966 Ishii et al. 26067 3,305,529 2/ 1967 Reynolds 26067 3,306,878 2/1967 Barton 260-67 3,027,352 3/1962 Walling et al. 26067 OTHER REFERENCES Novak et al.: Faraday Society Transaction, vol. 55, No. 441 (September 1959), pp. 1484-89.

Modena et al.: Journal of Polymer Science, part B, vol. 1, No. 10 (October 1963), pp. 567-570.

WILLIAM H. SHORT, Primary Examiner L. M. PHYNES, Assistant Examiner 

